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Title: Cooperative insertion of CO[subscript 2] in diamine-appended metal-organic frameworks

Authors:
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  1. (LBNL)
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Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
DOE - BASIC ENERGY SCIENCES
OSTI Identifier:
1178457
Resource Type:
Journal Article
Resource Relation:
Journal Name: Nature; Journal Volume: 519; Journal Issue: 03, 2015
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

McDonald, Thomas M., Mason, Jarad A., Kong, Xueqian, Bloch, Eric D., Gygi, David, Dani, Alessandro, Crocellà, Valentina, Giordanino, Filippo, Odoh, Samuel O., Drisdell, Walter S., Vlaisavljevich, Bess, Dzubak, Allison L., Poloni, Roberta, Schnell, Sondre K., Planas, Nora, Lee, Kyuho, Pascal, Tod, Wan, Liwen F., Prendergast, David, Neaton, Jeffrey B., Smit, Berend, Kortright, Jeffrey B., Gagliardi, Laura, Bordiga, Silvia, Reimer, Jeffrey A., Long , Jeffrey R., Grenoble), UMM), UCB), and Turin). Cooperative insertion of CO[subscript 2] in diamine-appended metal-organic frameworks. United States: N. p., 2016. Web. doi:10.1038/nature14327.
McDonald, Thomas M., Mason, Jarad A., Kong, Xueqian, Bloch, Eric D., Gygi, David, Dani, Alessandro, Crocellà, Valentina, Giordanino, Filippo, Odoh, Samuel O., Drisdell, Walter S., Vlaisavljevich, Bess, Dzubak, Allison L., Poloni, Roberta, Schnell, Sondre K., Planas, Nora, Lee, Kyuho, Pascal, Tod, Wan, Liwen F., Prendergast, David, Neaton, Jeffrey B., Smit, Berend, Kortright, Jeffrey B., Gagliardi, Laura, Bordiga, Silvia, Reimer, Jeffrey A., Long , Jeffrey R., Grenoble), UMM), UCB), & Turin). Cooperative insertion of CO[subscript 2] in diamine-appended metal-organic frameworks. United States. doi:10.1038/nature14327.
McDonald, Thomas M., Mason, Jarad A., Kong, Xueqian, Bloch, Eric D., Gygi, David, Dani, Alessandro, Crocellà, Valentina, Giordanino, Filippo, Odoh, Samuel O., Drisdell, Walter S., Vlaisavljevich, Bess, Dzubak, Allison L., Poloni, Roberta, Schnell, Sondre K., Planas, Nora, Lee, Kyuho, Pascal, Tod, Wan, Liwen F., Prendergast, David, Neaton, Jeffrey B., Smit, Berend, Kortright, Jeffrey B., Gagliardi, Laura, Bordiga, Silvia, Reimer, Jeffrey A., Long , Jeffrey R., Grenoble), UMM), UCB), and Turin). 2016. "Cooperative insertion of CO[subscript 2] in diamine-appended metal-organic frameworks". United States. doi:10.1038/nature14327.
@article{osti_1178457,
title = {Cooperative insertion of CO[subscript 2] in diamine-appended metal-organic frameworks},
author = {McDonald, Thomas M. and Mason, Jarad A. and Kong, Xueqian and Bloch, Eric D. and Gygi, David and Dani, Alessandro and Crocellà, Valentina and Giordanino, Filippo and Odoh, Samuel O. and Drisdell, Walter S. and Vlaisavljevich, Bess and Dzubak, Allison L. and Poloni, Roberta and Schnell, Sondre K. and Planas, Nora and Lee, Kyuho and Pascal, Tod and Wan, Liwen F. and Prendergast, David and Neaton, Jeffrey B. and Smit, Berend and Kortright, Jeffrey B. and Gagliardi, Laura and Bordiga, Silvia and Reimer, Jeffrey A. and Long , Jeffrey R. and Grenoble) and UMM) and UCB) and Turin)},
abstractNote = {},
doi = {10.1038/nature14327},
journal = {Nature},
number = 03, 2015,
volume = 519,
place = {United States},
year = 2016,
month = 6
}
  • Using a combination of density functional theory and lattice models, we study the effect of CO 2 adsorption in an amine functionalized metal–organic framework. These materials exhibit a step in the adsorption isotherm indicative of a phase change. The pressure at which this step occurs is not only temperature dependent but is also metal center dependent. Likewise, the heats of adsorption vary depending on the metal center. Herein we demonstrate via quantum chemical calculations that the amines should not be considered firmly anchored to the framework and we explore the mechanism for CO 2 adsorption. An ammonium carbamate species ismore » formed via the insertion of CO 2 into the M–N amine bonds. Furthermore, we translate the quantum chemical results into isotherms using a coarse grained Monte Carlo simulation technique and show that this adsorption mechanism can explain the characteristic step observed in the experimental isotherm while a previously proposed mechanism cannot. Furthermore, metal analogues have been explored and the CO 2 binding energies show a strong metal dependence corresponding to the M–N amine bond strength. We show that this difference can be exploited to tune the pressure at which the step in the isotherm occurs. Additionally, the mmen–Ni 2(dobpdc) framework shows Langmuir like behavior, and our simulations show how this can be explained by competitive adsorption between the new model and a previously proposed model.« less
  • In situX-ray absorption spectroscopy, coupled with DFT calculations, uncovers the details of the novel mechanism for CO 2adsorption in diamine-appended metal–organic frameworks.
  • Using a combination of density functional theory and lattice models, we study the effect of CO 2adsorption in an amine functionalized metal–organic framework.